Organo tin compounds and compositions containing same



ORGANO TIN coMPoUNDs AND c'oMros'irroNs CONTAINING SAME Ernest W.Johnson, Westfield, N. J., assignor to Metal & Thermit Corporation, NewYork, N. Y., a corporation of New Jersey No Drawing. Application July 7,1951, Serial No. 235,674

2 Claims. (Cl. 260429.7)

The present invention relates to a new organot-in mercaptide compound,the method of making the same and a resin composition containing theorganotin mercaptide as a stabilizer. In accordance with the presentinvention, a new compound has been developed classified as an organotinmercaptide and having the formula RnSn(SR)4-n, in which R is a group ofthe class consisting of an alkyl, aryl and hetenocycle in substitutedand unsubstituted form, R' is a group of the class consisting of alkyl,aryl and heterocycle in. substituted and unsubstituted form and n is anumber from one to three. The R groups and the R groups need not all bethe same.

The organotin mercaptide of the present invention is particularly usefulas a stabilizer for vinyl resin and is also useful as a rubberaccelerator, rubber anti-oxidant, lube oil additive and polymerizationaccelerator. In connection with vinyl resin, it has been found that theorganotin mercaptide of the'character described when added to the vinylresin in amounts equivalent to 0.5 to 10.0 parts by weight of stabilizerto 100 parts of the resin is effective as a stabilizer. However,for'commercial use, 1.0 to 3.0 parts by weight of stabilizer to 100parts by weight of resin is preferred.

1 have found that org-an-otin oxides (RzSnO), organotin hydroxides(RaSnOH) and 'stannOnic acids (RSnOzH) will react with primary,secondary and tertiary mercaptans to yield derivatives of the typesR2Sn(SR)2, RaSnSR' and RSn(SR')3. The reactions for such preparationsare as follows:

In accordance with another process for preparing these derivatives, thestarting material is an organotin halide. It has been determined inaccordance with the present invention, that organotin halides such asRsSnX, RzSnXa and RSIlXs will react with m-ercaptan in the presence ofearth metal oxides, hydroxides, bicarbonates and carbonates, andspecifically sodium hydroxide or sodium carbonate to yield the sametypes of derivatives through the replacement of the halide group by theSR group.

The following examples illustrate certain ways in which the organotinmercaptide of the present invention can be prepared:

Example I basic HCl acceptors, such as alkali metal and alkaline niteclStates Patent "ice weighed 85.5 g. and by analysis contained 33.5% Snand 16.9% S.

Example II One-half mole of normal butyl mercaptan, one' qu'ar'tei'niole of dibutyltin oxide and 200 ml. of toluene were heated to reflux.The water of reaction was removed by the use of a moisture trap.Solution of the oxide occurred before all the water was removed. Afterremoval of the water, toluene was stripped out by use of a downwardvacuum distillation to yield a final nearly odorless residue. Thisliquid residue weighed 99.7 g. and contained 28.7% Sn and 15.0% S.

Example III One-half mole of isobutyl mercaptan, 0.25 mole of dibutyltinoxide and 200 ml. of toluene were refluxed with stirring until solutionof the oxide occurred and the theoretical water was obtained. Thetoluene was vacuumstripped to leave a light colored liquid product whichanalyzed 28.8% tin and 15.2% sulfur.

Example IV 0.198 mole of sec. butyl mercaptan (prepared from sec. butylbromide and thioureau by a modification of the process by Urquhart andco-workers, (Organic Synthesis, vol. 21, page 36, John Wiley & Sons, NewYork (1941)), and 0.099 mole of dibutyltin oxides were heated with 200ml. of toluene until the theoretical water was removed. The toluene wasstripped and a light liquid product resulted. Analysis indicated 28.2%Sn and 14.6% S.

Example V One-half mole of n-amyl mercaptan, 0.25 mole of dibutyltinoxide and 200 ml. of toluene were heated (with mechanical stirring) toreflux. The oxide was completely dissolved after 20 minutes of heating(temperature had only reached 91 C.), while the water was distillingover into a Barrett moisture trap. After the theoretical water (4.5 ml.)was removed, heating was continued for 2.5 hours. The solution was thencooled, filtered and stripped of solvent to a pot temperature of C. at apressure of 2 mm. The product was a light colored liquid weighing 106.9grams. Analysis indicated 26.9% Sn; 14.6% S.

Example VI 0.088 mole of triphenyltin hydroxide, 0.088 mole ofpredominately lauryl mercaptan, hereinafter referred to as laurylmercaptan, Hooker (Hooker Electrochemical Companys product whichapproximates C13H27SH, being a mixture of normal C10, C12, C14, C18mercaptans, with C12 predominating), and 50 ml. of toluene were heated(stirring) to reflux. After removal of the water of reaction, themixture was cooled, filtered and filtrate stripped of solvent. Theproduct weighing 37.8 grams contained 18.9% Sn and 6.0% S.

Example VII One-half mole of n-amyl mercaptan, 0.25 mole of dilauryltinoxide and ml. of toluene were heated and stirred at reflux. After thewater was removed, the mixture was cooled, filtered and stripped. Theproduct was a light colored liquid weighing 80.2 grams, contained 17.4%Sn and 9.6% S.

Example VIII One-half mole of n-hexyl mercaptan, 0.25 mole of dibutyltinoxide and 200 ml. of toluene were heated to reflux. After the water ofreaction was removed, the mixture was stripped of solvent. A residuallight colored liquid was obtained in 97% yield. Analysis showed 25.2% Snand l3.5% S.

Example a Example X One-halt mole of n-heptyl mercaptan, 0.25 mole ofdibutyltin oxide and 200 ml. of toluene were heated to reflux, the waterof reaction removed, and the mixture filtered. After stripping to atemperature of 115 C.

a and a pressure of 2.5 mm., the filtrate left a very light coloredliquid residue (125.2 grams) which analyzed 23.8% Sn and 12.6% mercaptosulfur.

Example XI- One-half? mole n-octyl mercaptan, 0.25 mole of dibutyltinoxide and 200 ml. of toluene were treated as'in Example X. The productwas a light colored viscous liquid weighing 135.9 g. The theoreticalyield is 130 grams. The extra 5.9 grams arise fromthe mercaptan used.Most of the mercaptan used in this specification were assayed by aniodimetric titration and a quantity of the assayed mercaptan sufficientto give the desired mole quantity of titratable mercapto group(equivalent to the organotin compound) was then taken. Thus, the n-octylmercaptan used above assayed 89.2% titratable mercaptan. A weighedquantity was taken, suflicient to contain just one-half mole oftitratable SH. Analysis of the product indicated 21.5% Sn and 11.6% S.

Example XII Dibutyltin oxide (0.162 mole, 40.3 grams), n-nonyl mercaptan(99.5% by assay; 0.325 mole; 52.0 grams), and toluene (170 ml.) weretreated as described in Example X. The product weighed. 85.5 grams andcontained 21.5% Sn and 11.2% S.

Example XIII Dibutyltinoxide (0.25 mole, 62.1 grams), n-decyl mercaptan.(94.1% by. assay; 0.5 mole; 92.6 grams), and

toluene (200 ml.) were allowed to react as described in.

Example X. The product weighed 149 grams; it was a viscous light coloredliquid containing 19.5% Sn and 10.6% S.

Example XIV Example XV One mole, 202.0 grams, of tertiary laurylmercaptan in 100 ml. of toluene was added to 40 grams (1 mole) ofsodiumhydroxide in 50 ml. ofwater. To this mixture was added 0.5 mole(151.8 grams) of dibutyltin dichloride in 200 ml. of toluene. Themixture was stirred andheated to distill out the water azeotropically.After removal of the water, the solution was filtered hot to remove thesodium chloride formed (the NaCl forms large crystals in this process).The filtrate was cooled, filtered, and vacuum stripped .to removesolvent. At a final temperature of 130 C. at 3 mm. pressure,.productWasa light colored liquid weighing 287.7 grams. Analy.-

sisindicated' 18.7% Sn, trace of Cl.

Example XVI 91.1 grams of dibutyltin dichloride and 127.7 grams oflauryl mercaptan, Hooker were heated to 65 C.

in a stirred stainless steel beaker and 42 grams of anhydrous sodiumcarbonate was added over a 6-minute period. The temperature rose to 83C. during this time and was held there for 1%. hours. The mixture wasfiltered, and the product was a clear light colored liquid. Analysisshowed 18.0% Sn, 9.7%'S, 0.05% CI.

Example XVII One-half mole of lauryl mercaptan, Hooker, 0.25 mole ofdimethyltin oxide, and ml. of toluene were refluxed and treated as inExample X. The product was a light colored liquid with an analysis of19.7% Sn and 10.7% S.

Example XVIII One and one-half moles of lauryl mercaptan, Hooker, 0.5mole of methylstannonic acid and 200 ml. of toluene were used in theprocess of Example X. The product was a light colored liquid, weighed360.7 g. and contained 15.0% Sn and 12.0% S.

Example XIX One-quarter mole of; lauryl mercaptan, Hooker, 0.25 mole oftrimethyltin chloride and 100 ml. of toluene are heated'to 65 C. as inExample XVI. Anhydrous sodium carbonate (5'3 grams).is then added to themixture. Caution: This reaction must be carried out in an efiicient hoodas the trimethyltin chloride is very noxious. The reaction mixture isfiltered hot and stripped of solvent.

Example XX One-half mole oflauryl" mercaptan, Hooker, 0.25 mole ofdiphenyltin oxide and 200 ml. of toluene are treated'as describedinExample X.

Example XXI One-quarter mole of triphenyltin chloride, one-quarter moleof lauryl mercaptan, Hooker, 100 ml. of toluene and 53 grams of sodiumcarbonate are treatedas described in Example XIX.

Example XXII Diamyltin oxide (0.122 mole, 37.6 grams), 0.244 mole oflauryl mercaptan, Hooker, and 100 ml. of toluene were treated asdescribedin- Example X. The clear light colored liquid productweighed-70.6 grarns'andw analyzed 17.0% Sn and 8.7% S.

Example XXIII One-quartermole ofdi'lauryltin oxide and 0.5 mole oflauryl mercaptan, Hooker, yielded 2.12.6 grams of light colored liquidproduct. Analysis. indicated 13.0% Sn and 6.9% S.

Example XXIV One-half mole. of methyltin. trichloride, 1.5 moles oflauryl mercaptan, Hooker, 200 ml. of toluene and 318 grams of anhydroussodium carbonate are treated'as described in Example XIX.

Example XXV One-quarter mole of' trimethyltin hydroxide, onequarter molelauryl mercaptan, Hooker and 100 ml. of toluene are treated by theprocess of Example X.

Example XXVI One-quarter mole of tributyltin hydroxide, one-quarter moleof lauryl mercaptan, Hooker? and 100 ml. of toluene are treated asdescribed in Example X.

Example: XXVI] Example XX VIII One-quarter mole of ethylstan'nonic acid,0.75 mole of lauryl mercaptan, Hooker and 150 ml. of toluene are treatedby the process of Example X.

Example XXIX One-eighth mole of diphenyltin oxide, one-quarter mole ofbenzylmercaptan and 100 ml. of toluene were treated by the process ofExample X. The product contained 22.4%. Sn and 12.4% S.

Example XXX One-quarter mole of dilauryltin oxide, one-half mole ofbenzylmercaptan and 150 ml. of toluene were used in the process ofExample X. The product contained 16.1% Sn and 9.2% S.

Example XXXI Dibutyltin oxide, 41 grams, n-tetradecyl mercaptan (88.6%SH), 85.5 grams, and 150 ml. of toluene were carried through the processof Example X. The product 5 analyzed 15.7% Sn and 8.85% S, and weighed123 grams.

Example XXXII Dibutyltin oxide, 40.8 grams, n-hexadecyl mercaptan(95.2%), 88.8 grams and 145 ml. of toluene were treated as in Example X.The product weighed 126 grams. Analysis indicated Sn, 15.1%; S, 8.3%.

Example XXXIII Dibutyltin oxide (0.38 mole), ter-hexadecyl mercaptan(0.76 mole) and 350 m1. of toluene were treated by the process ofExample X. Product weighed 265.2 grams; analysis showed Sn, 14.8%.

Example XXXIV Dibutyltin oxide (0.25 mole), thiophenol (0.50 mole) and200 ml. of toluene were treated as in Example X. The product was acolorless liquid, weighing 110.5 grams. Analysis showed 26.4% Sn.

Example XXXV Dibutyltin oxide (0.218 mole), p-thiocresol (74% 0.435mole, 73 grams), and 150 ml. of toluene were treated as describedinExample X. The light colored liquid product weighed 104.6 grams andcontained 23.9% Sn and 13.45% S.

Example XXXVI Dibutyltin oxide (0.25 mole), 2-aminobenzenethiol (0.50mole), and 200 ml. of toluene were treated as in Example X. The productwas a dark colored liquid weighing 112.2 grams. Analysis indicated 25.6%Sn and 12.2% S. It required considerable treatment with decolorizingcarbon to be purified sufliciently to be useful as a stabilizer incolorless vinyl chloride sheetings.

Example XXXVII Dibutyltin oxide (0.5 mole), Z-mercaptobenzthiazole I, (1mole) and 350 ml. of toluene were treated as previously described. Theproduct was a light tan solid weighing 275 g. Analysis showed 21.0% Snand 22.2% sulfur .(by combustion). Recrystallization from 50/50alcohol/acetone yielded a light colored crystalline product. A generaltest method was used to test effectiveness of most of the products fromExamples IXXXVII as stabilizers for polyvinyl chloride resins. The resinused was Geon 101 (produced by the B. F. Goodrich Co.) unless otherwisespecified.

The stabilizer was incorporated into a mixture of 100 parts by weight ofresin and 50 parts by weight of a plasticizer (here Flexol DOP (dioctylphthalate)). The weight of stabilizer was determined by its analysis.Thus enough stabilizer was used to provide the same weight The mixturewas then milled for 5 minutes on a tworoll differential speed millheated to 320-325 F. and removed as a sheet. Portions of the sheet werethen placed in a single cavity mold (6" x 6" x 40 mils) preheated to 275F. The mold was placed on a press and raised to 320 F. under 10,000pounds total pressure. When the mold reached 320 F., the pressure wasincreased to 40,000 pounds and held until the temperature reached 330 F.This procedure required 5 to 5 /2 minutes. The mold and press platenswere then cooled and the pressed sheet removed.

The pressed sheet was cut into 1" x 6" strips and placed in clips on atray so that the strips would hang vertically. The tray was then placedin a circulating air oven held at 320 F. Samples were removed after onehour, two hours, three hours and four hours of heat aging. Samples wererated visually. Summary of the tests are indicated as follows:

SUMMARY TABLE Code: c, colorless; vsy, very slight yellowing; sy, slightyellowing; y, yellowed; rbr, reddish brown; br, brown; b1, black, ble,black at edges.

Appearance after heat agmg 1 2 3 4 Hr Hrs. Hrs. Hrs.

Stabilizer from Example N0.:

N0 stabilizer rbr bl Dibutyltin dilaurate y rbr b1 bl (2 parts/ parts ofresin) Example 1 c vsy vsy sy Example 2. c vsy vsy sy Example 3. vsy vsyvsy sy Example 4. sy sy sy y Example 5. vsy vsy sy sy Example 6. sy sy y37 Example 7 sy sy sy y Example 8 vsy vsy vsy sy Example 9. sy sy sy syExample 10. vsy vsy sy sy Example 11. vsy vsy sy sy Example 12 vsy vsyvsy sy Example 12 in Geon 202 resin, a copolymer of vinyl chloride andvinylidene dichloride sy sy sy sy Dibutyltin dilaurate in Geon 202 0y 0yb1 b1 Example 12in VYN W resin, a copolymer of vinyl chloride and vinylacetate. sy sy y rbr Dibutyltin dilaurate in VYN W resin- 0y bl bl blExample 13 vsy vsy vsy sy Example 14. vsy vsy vsy sy Example 15. vsy vsysy sy Example 16.-. vsy vsy vsy sy Example 17. 4 grey grey grey grey inUltron 300 resln (polyvinyl chloi e c c vsy in Geon 101 EP resin c c evsy Example 18 c c vsy vsy Example 22. vsy vsy vsy sy Example 23 vsy sysy sy y Y Y Y c c vsy y c vsy vsy sy c vsy sy y ight gray tint vsy vsysy sy Example 31 vsy vsy vsy sy Example 32. vsy vsy sy sy Example 33.-.vsy vsy sy sy Example 34 vsy vsy vsy sy Example 35. vsy vsy vsy vsyExample 36- sy sy br bl Example 37 sy sy y y Further tests were carriedout to determine the heat stability of vinyl films containing aphosphate plasticizer and stabilized with an organotin mercaptide of thepresent invention. The results of these tests are indicated in the tablebelow. In this table, 0y indicates orange yellow, rbred brown, and S-141an aryl, alkyl phosphate plasticizer.

p KppearanceAfter Heat Aging. Eflmc Composltlon Resultsz: Film 3Composition h 1 5 1 Hr; 2' Hrs. 3 Hrs. 'i'Hrs. 100 pts;.GEQN:l01-.-Speaking at: 5001 std, Fading- 5 40 pts. D]? Hours. No embrittlemeut E10 pts. G-25; and only slight general dis- 100 partsGeon 101 1 pt.Dibut'yltin d1 coloration at 1,000 Std. Fad- 35 parts DOP thiocresol.ing Hours. A 15 parts S-141 e vsy vsy y 100'pts. Geon 101 2' partsdibutyltin d1-' .40 pts.:DOP

lauryl mercaptide. F pts. (3-25 Like Film E. 100 parts Geon 101 1 pt.Dimethyltln' di I 35 parts DOP 10 tert-laurylmercaptlde. l3 partsS-1'41' c vsy vsy vsy 100 pts. Geon 101 Specking at 600 Std. Fading 2parts Dimethyltin di- 40 pts. DOP Hours. No embrittlementtert-laurylmercaptlde. G 10 pts. G25* and only slight general dis- 100parts Geon 101; A 1.- pt. Dlbutyltin di.- coloration at 1,000, Std.parts DOP 1 lauryl mercaptlde: Fading Hours; 0 20 aws-141 3* 0y 100ptsrGeon 101,.

2 parts Dibutyltin di- 1 laurate. Like Film G. 100 parts Geon 101 d137.5 parts DOIL lauryl mereaptlde. D 12.5 parts S 141 -T y 0y rb 100pts. Geon 101 2.0 parts Dibutyltifi di- 40 pts. DOP lam-ate. I 10ptsuG-ZS, Like FilmG.

1 pt. Dlamyltin di- If i 2O lauryl mercaptlde. For films containingphosphate plasticizers, the results 1 shown are much better than wouldbe obtamedusing wpammxs gpplasmlzen madabyRohm and Haas and consistingother stabilizers. For example, using the formulation of esswtially 9fpolyesters 1 film A but Substituting 2 Parts of dibutyltin dilaurateWhile the invention has been described with particular tWO Parts ofdibllt'yl'iln dllaulyl mercaptlde, the results reference to specificembodiments, it is to be understood of the h tests were: 1 y; 3 that itis not to be so limited thereto but is to be con- 'hT strued broadly andrestricted solely by the scope of the Tests were carried out todetermine the stablhty of d d l i vinyl films to light Whencompoundedwith an organotiri Wh i l i of the present invention. For that purpose,the films of 1. Dibutyltin di(2-benzothiazyl) mercaptide. 5 milsthickness were exposed to the accelerated light 2, Pro e which comprisesheating dibutyltin oxide action of an Atlas fadeorneter. The results ofthese tests ith Z-mercaptobenzothiazole.

are as follows:

References Cited-in the file of this patent UNITED STATES PATENTS2,258,718 Rothrock Oct. 14, 1941 2,344,002 Rugeley et al. Mar. 14, 19442,376,313 Reiff May 15, 1945 2,431,038- Harris Nov. 18, 1947 2,480,823Morris Sept. 6, 1949 2,481,086 Cleverdon et al. Sept. 6, 1949 2,489,518Burt Nov. 29, 1949 OTHER REFERENCES

1. DIBUTYLTIN DI(2-BENZOTHIAZYL) MERCAPTIDE.
 2. PROCESS WHICH COMPRISESHEATING DIBUTYLTIN OXIDE WITH 2-MERCAPTOBENZOTHIAZOLE.